Tertiary diacyl amine insecticide



Patented Mar. 13, 1951 UN [TED STATES PATENT OFFICE I 2,545,287- p I TERTIARY DIACYL SEETICIDE James E. Kirby, Wilmington, Dell, assignor to E. L-du Punt -de Nemours &;Gompany,"*WiI- mington, Del a corporation of Delaware NoDrawing. ApplicationrOctnber 10, 1945, Serial N0. 621,595

.4 Claims.

This invention relates to pest control and' is particularly directed to methods andcompositions for preventing or-arresti'ng infestations of insects which are economically harmfultoman and which commonly infest organic matter whether-plant orani-mal or plant oranimal origin either-in-its natural, fabricated, or synthetic-state.

'More specifically my invention relates to 'inr secticidal compositions and methods which are characterized by the use of tertiary amines of the type derived I from=difunctional =otganic acids and a primary amine *and having two valences o-f nitrogen attached to acdiacyl radical, which tertiary amines are referred to herein 'astertiary diacyl amines. V I

This case is a -continuation-ini-part of my copending application, Serial No. 501,137, filedSep tember 3, 1943, now abandoned. r

The invention has: :as: object. the provision of :new insecticidal compositions :and methods. Aiurtherobject is to provideznewcompositions andmethodsxwhitzh when employed -inconnection with; other; insecticida1, agents such asnyrethrum increase the efiectiveness of :the othenins cticidal agents. A still :further rob-31 261 is: to providenew compositions and methods -.efiecti-ve for, repelling mosquitoes and. other dipterous insects. Other objects-will appear hereinaften.

According to the, present inventionsthesefobjects are accomplished by bringing into' contact with the insect pest the compositions- ,of thein vention, which cqm-positionsgcontain as :an (essential active ingredientone or .more tertia y diacyl amines.

The tertiary ,diacylcamines employed ;according to the present invention may berobtained byyrelacting, a. suitable difunctionalacidwwithi a primary amine under conditions appropriate :tolring; .010.- sures. Theyiare imidesof prima faminesn They specifically distinguish ;from secondary I diacyl amines, which are the unsubstituted {-imides; by not havingiaihydrqgen attached; .to--.the-ini;trogen atom. This hydrogen of the secondary d-iacyl amine is highly activated by reason -:Qf itsposition,r.alpha, totwoistrongly negative groups.

Thetertiary diacyll, amines, may be (represented by the formula 2 in which is a diacyl radical and R. is the radical' ofthe primary amine. X and Y are the'acyl determinants which may be thesame or different and are selected from such radicals as propyl, .n-isolcutyl,- n-butyl, -n-amyl,. mixed iamyl mheptyl, ni-oxtyl, -n-dodecyl, cyclo'hexyl, benzyl, phenyl,.ortho-ethozqzphenyl, ortho-xylyl, orthotolyl, mixed .orthometawand .paraatolyl, paradodecylphenyl, ortho-mtrophenyl, meta-nitrophenyl,=para -nitrophenyl,.orthor-biphenylyl,parabiphenylyl, :2 -ethy1hexyl, (11,3-phenylene)di-, 2(4-phenylthi'azolyl), alpha-naphthyl, S-chloro- 2;4-hexadienyl', methall yl, -allyl,-beta-h-ydroxyethyl-,beta-cyanoethyl,- omega-cyanopentyl, "5,5,5- trichloro-Z-pentenyl, and vinyl. 7

Primary amines such as listed above-may be reacted-under appropriate conditions with a wide variety of acids, "afcid anhydrides, or certain cases acyl l 1jalides to give-"the imid'es suitable for use 'thecompositions and methods of the invention; Forexample, such i-mides may beprepared from ,succinic, phenyl'succinic, .glutaric, mal'eic, phthalic;tetraghydrophthalic, hexahydrophthalic, jhomophtha'lic, quinolinic and cincho- 1116101110, glutaoonic, thiodiglycolic imino'diacfit' jc, die yccl c N+ c1 h "iminc'diacet' cci r 'c, dihydrophthalic', 3g6 endomethyleneei-cyelohexene-1 ,'2-dicarbo 5y1i c, 316-endoetlrylene-4iQ-cyplohexene -lzZ-dicarbo gylic,o diphenic, aconitic, citric,

tricarballylic', and itaconicaci'ds,

interacti n cinflmam minesand select d a i their appropri t dcr vatives Thus the P16- ierre tync te t ary d acy am ncsa ejthc in whi'ch'R. of the diacyl group -;XR*Y is an organic radical linking X and Y together by a carbon chain of preferably two but not more than three carbon atoms. Such diacyl groups are characteristic of the following typical acids: succinic, phenylsuocinic, glutaric, maleic, citraconic, mesaconic, pyrocinchonic, ethylmethylmaleic, aconitic, citric, tricarbollylic, itaconic,

amass? glutaconic, dithiosuccinic, phthalic, dihydrophthalic, tetra-hydrophthalic (4-cyclohexenc- 1,2-dicarboxylic), hexahydrophthalic (cyclohexane-1,2-dicarboxylic), homophthalic, quinolinic, cinchomeronic, 3,6 endomethylene 4 cyclohexene-l,2-dicarboxylic, 3,6-endoethylene-4-cyclohexene-1,2-dicarboxylic and 3,6-endomethylene cyclohexane 1,2 dicarboxylic, 3,6 endo methylene 2 methyl 4 cyclohexene 1,2 dicarboxylic, 7 methyl 3,6 endomethylene 4 cyclohexene 1,2 dicarboxylic, 3 methyl 4 cyclohexene 1,2 dicarboxylic, 3 methyl 6 carbobutoxy 4 cyclohexene 1,2 dicarboxylic and 3,6 endoethylene 3 isopropyl=- 6 methyl- 4-cyclohexene-1,2-dicarboxylic.

Other suitable imides include those derived from dithiosuccinic, morioand di-thiophthalic, orthosulfobenzoic, ortho sulfophenylacetic, ethane disulfonio, beta-sulfopropionic acids.

The acids having orthofunctional groups are preferred for use in the preparation of the imides suitable for use in the compositions and methods of this invention because they give the -membered diacyl amine ring structure.

Succinic, glutaric, maleic and glutaconic acids are typical of the acyclic acids which give monocyclic compounds. From these 5- and G-membered saturated and Unsaturated diacyl amino ring structuresare obtainable; Such structures as are obtainable, for example, from acids of the maleic acid and glutaconic series are preferable because of the ethylenic unsaturation in the carbon'chain linking the two functional groups. In forming imides from these ac clic acids, it is desirable to use an amine which also is acyclic, and preferably an alkyl amine containing less than 12 carbon atoms. I

The, phthalic acids, the reduced phthalic acids, the pyridinedicarboxylic acids and the alicyclic dicarboxylic acidsfllisted aboveare typical of cyclic acids which may beused in producing polycyclic compounds according to the invention. The cyclic acids may be carbocyclic or heterocyclic but preferably are alicyclic ortho-dicarboxylic acids. Non benzenoid unsaturation in these alicyclic ortho-dicarboxylic acids is desirabl and particularly when such unsatur'ation is gamma, delta to the functional acyl group. The alicyclic group is preferably bicyclic and made up of two fused 5-membered rings as in the case of (2.21) ,bicyclo-4-heptene-1,2-dioic acid ("3,6-endomethylene-4-cyclohexene-l,2-dicarboxylic acid). In producing i'mides from these cyclic acids it is desirable to use acyclic amines, especially alkyl amines containing less than 8 carbon atoms.

By selecting suitable acids and amines as outlined above there may be obtained a wide variety of compounds "suitable'foru'se according to the present invention whichin general may be either solids or oils and stable, colorless, relatively odorless, insoluble in water'and soluble in most organic solvents such 'as acetone, alcohol, ether, benzene, kerosene and certain other hydrocarbon solvents. In general, such compounds may be prepared as described above and mor particularly illustrated below by the interaction of the appropriate acid ester oranhydri'de with the de- '3 I sired amine either alone or in the presence of solvents such as benzene or other indifierent solvents;

SCHEME 1 Preparation of the N-(n-but'yl) imide of 3,6-

endomethylene-4-cyclohexene-1,2 dicarbomylic acid N- (0 Hz) a 0 Ha I 0 I surface of a mixture of 98 g. of maleic anhydride and 200 cc. of benzene at ordinary room temperature and injecting the cyclopentadiene as rapidly a is consistent with adequate reflux to prevent loss of reactants. This operation is complete in 15-20 minutes. I

Seventy-three grams of dry n-butylamine is then added as rapidly as reflux capacity will permit. Water is removed from this mixture in an apparatus for refluxing and distilling, separating the water and returning the benzene to the reaction pot. After removal of 16.5 cc. of water by this procedure, the benzene is distilled from the product leaving a residue with an acid number of 9.5. This crude acidic material, amounting to 214 g., is purified by direct distillation or by first alkaline scrubbing and then distillation. A satisfactory product for insecticidal use is obtained by scrubbing the crude acidic material with a slight excess of the theoretical amount of 5% sodium hydroxide solution, which results in a loss of approximately 6-8% in the weight of the product. This substantially neutral product is on further purification by distillation from a modified Claisen flask found to possess a boiling point of 134-137 C./2 mm., giving 186 g. of a colorless oil which soon solidifies to a white solid, melting at 42-44 C. (11, -=1.5030) Alternately, the intermediate anhydride of the above 3,6-endomethylene 4 cyclohexene 1,2- dicarboxylic acid may be prepared by heating under reflux a mixture of 66 grams of dicyclopentadiene and 98 grams of maleic anhydride at C. for 4-5 hours. Other analogues are produced by-substituting for n butylamine such amines as methyl, ethyl, propyl, isopropyl, isobutyl, n-amyl, mixed ,amyl, n-heptyl, n-octyl, n-dodecyl, cyclohexyl, benzyl, phenyl (aniline), ortho -ethoxyphenyl, orthoxylyl, beta-hydroxyethyl, beta-cyanoethyl, allyl and omega-c'yanopentyl amines. Similarly other analogues are produced by substituting for the cyclopentadiene other dienes which react with maleic acid to give alicyclic ortho-dicarboxylic acids such as 3,6-endomethylene-cyclohexane- 1,2 dicarboxylic acid, 3,6 endomethylene 2- methyl 4 cyclohexene 1,2- dicarboxylic' acid, 7-methyl-3,6- endomethylene-4-cyclohexene-1,2- dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 3-methyl 4- cyclohexene-1,2-dicarboxylic acid, 3-methyl-6-carbobutoxy-4-cyclohexene-1,2-

, 8' Theiollowing are typical-of such analogues.

'FDABilIEJI min, Found N, 6. 7

Imides of 3,dmdoethylemfi-isoprqgyl-giemetiryleiseycloharem-Lt-dz'carbofcxjhb acid N-methyl, Found N, 3.87%

N -a.1 1yl FoundiN, 432% N-n-butyl, Found N, 4.61%

N -cyclohexyl, Found N, 434% N-n-dodecyl, Found 'N,'3;34%v N-phenyl, Found N, 3.90%

Aproprietary -produot' consisting ofam-irture oiizarious isoniers as tert.-amy1, se'c..-an 1yl, isoamyl, n-alnyl, actlve-amyl a-mmesand :2- and 3-amino pentane.

Erezmration f N phenylmaleimid N.-phenylmaleamic acid was prepared by ,s't'irring 186.2 grams of aniline into .a..s o1ution of 1982 grams of maleic anhydride-in 1500 cc. of chloroform at 110.20 C. Stirring was continued for minutes. and .a .paleyelldw cwder meltin at 299-210.? C. was recovered. by filtration, washing and drying. A mnitureofjfi'lA g. (0.3 mole) of n-phenylmaleamicacid .(maleaiiiilic acid) 10 g. (0.12;-mole) .oi .fusedsodium acetate, and 102.1 g. (1 mole), of acetic anhrdridewas heated with stirring on a steam bath. Whenthe temperature of the mixture had reached 80 C.

5 Nalnta all of the .N-phenymaleami'c acid had .goneiinto solution and the bath was dropped. The temperature continued to rise to a maximum of"92 C. from the heat of the reaction. The reaction mixture was allowed to cool to room temperature (one hour) and then poured 'sl'owly int'o a stirred ice-water slurry (800 .00.). The yellow crystalline precipitate was filtered off; washed Well with water, and dried in vacuo over P295. The yield was 44 g. (8.5%.) of yellow 'oliystallme powder meltin at :1 r

Other analogues areproduced by substituting for the aniline .suc'h amines :as .ne'dodecyLpethoxyphenyl, alpha-naphthyl. o-tolyl, m-tolyl, .p-tolyjl, mixed 0-. m-. and p-tolyl, p-dodecyl- ,phen-yl, .o-n itropheny1 nitrophenyl, p-nitro- 'henyl, .o-hiphenylyl, .p-hmheny y a-eth lh y amines and (1;3+phenylene) -diamine. Similarly :other analogues. areproduced by substituting 12 :maleic anhydr-ide various otheracids of the .maleic acid series or their annydrides. -S. l 1 h o c, me aconi tyres chonic (dimethyl maleic) "ethyln'iethylmal-eic, aco'n'itic. etc. I

. N v ny e, M. N -.c-. thoryph ylphth inn .e, -.P-.. .3.1 e Q. ound N. N-3 loro-2,4-hekadienylphthalimide, M. P. 119-120" 0., Found N,

534 7 Ngl nigg d'amylhomophthalimide. .B. :P. 51.639168 0J3 1pm., Found I. am aware that various 'imicl'es have -beensuggested as insecticides, fungicides; .or bactericidesa but I .am not aware that the tertiary diacyl amines employed in'the compositions and methods oi this invention have everbeen considered to be. or thought. to "be. or suggested to be of value for the control of insect pests. Thus in .U. S. Patent 2,205,558 imides of maleic acid are w ested' as bactericides and fungicides. Bactericides-and fungicides. however, are a different field from thatgof the present invention and :compounds as a rule useful in one are not useful in the other. InU'. Patent 2.119.701 .mercuriated imi'des are suggested as disinfectants and fungicides. These compounds, "however, are salts of secondary diacyl amines. "In "U. S. Patent 1961340, "2,4-diketo-tetrahydrothiazole is disclosed to have insecticidal, properties. Also, in British Patent 407,356, there are disclosed certain mixed carboxylic and sulfonic acid imides =asingredients= of mothproofing compositions. In those of the above compounds disclosed as insect toxicants, the N-hydrogen is alpha to two strongly negative carbonyl groups and as such has saltforming properties possibly by reason of the fact that the hydrogen wanders, yielding a tautometr-ic-enol form.

In S; Dept-poi Agriculture Circular No. 523 on the Toxicity of certain Organic Insecticides to Codling- Moth Larvae Laboratory Tests there .is. .reported inconclusive tests of phthal imide as codlingmoth control. In ,the Journal of industrial and Engineering :Chemistry 19, 1"115 "("1927'). potassium phthalimid'e is reported ineffective for .mothproofing. theJournal 01, 'Economic Entomology 33', 669' (19510)- nitro and bromo phthalimides are reported ineffective againstscrew-Worms and $.5Dfilgt. of Agriculture Bulletin-No. 1160- Studieson-Eontact Insecticides suceinim-ide is reported' ineffective easiest againstAphismumicis- The imidespf thesepub- I licatiofis, unlike the ir'n'ides er the invention,"are characterized by a highly reactive N-hydrogen. Moreover, the teachings of these publications are essentially negative. 7 Y The compositions of the inventionare particularly useful as fly sprays preferably as solutions of tertiary diacyl amines in arefined kerosene fly spray base, as mosquito repellents,-delousing agents, for the control of bed bugs, and for the control of similar pests. r

Heretofore the control of such pests as flies; for example, particularly in the household, has been effected almost exclusively by pyrethrum fly sprays. For the past several years efforts have been made to introduce organic thiocyanates intothis field but-without much success untilthe current emergency restricted supplies of pyrethrum. These thiocyanate sprays, however, while effective, do not have the desirable characteristics of pyrethrum sprays and are tolerable in household sprays only under the conditions of the war emergency. Even so, there are applications which require pyrethrum in which the organic thiocyanates are undesirable. synergist, sesame oil, is required in the new aerosol sprays and pyrethrum activated by a syner gist, N-isobutylundecylenamide, is required in delousing. Materials therefore which will step up efficiency of the pyrethrum insecticides or replace part of the pyrethrum arev much needed to con serve our limited supply of pyrethrum.

The tertiary diacyl amines are such materials.

They increase the efiiciency of pyrethrum insecticides in varying degrees according to the par ticular imide employed and in the same measure permit reduction in pyrethrum content. Some of the more effectivematerials, such as thefnbutyl and n-amyl imides of 3,6-e'ridorr1thylene- 4-cyclohexene-1,2-dicarboxylic acid, are substantially more effective in being able to displace pyrethrum in fly sprays than such known synergists as N-isobutylundecylenamide.7

Pyrethrum fly sprays contain a minimum of 100 mgs. pyrethrins per 100 cc. of fly spray base oil such as a refined kerosene. Such is the composition of the ofiicial test insecticide .used asfa standard of comparison in the industry. According to this invention it is possible to replace as much as 90% or. more'of the pyrethrins with a suitable imide and stillcbtain the same paralytic and lethal eifects, and'to replace as much as 95% FLY SPRAY- TESTS ON. R

Thus pyrethrum activated by a or more of ,the pyrethr ins and still. obtain the same lethal effect'without excessive reduction of paralytic effect. Preferred compositions according to the invention accordingly may contain from about 5 to about mgs. pyrethrins together. with considerable quantity of the imide dissolved in a fly spray base.

In such compositions, using the more active imides according to the inventiomresults comparable to the official test insecticide may be obtained by replacing pyrethrum by imides' in the ratio of approximately 10 parts of imide for each part of pyrethrum replaced. The compositions of the invention accordingly may contain as-a bare minimum from about 5 to aboutlOOmgs. pyrethrumper 100 cc. fly spray. and at least'from about 10 (100-P) mgs. imide per 100 cc. fly spray, where P equals mgs. of pyrethrum per 100 cc. fly spray with maximum of imide limited only by the solubility of the imide in the fly spray base.

It is frequently the practice in the art to manufacture a composition containing the active in gredients of the formulation in larger amounts than would normally be utilized in a fly spray, such composition being called a concentrate. Such compositions, or concentrates, are so formulated that by a proper and usually predetermined degree of dilution of the concentrates of class AA, class A, or class B insecticide maybe produced as desired. When it is desired toproduce as a concentrate a composition of this invention containing pyrethrum and an imide, the amount of pyrethrum and the preferred minimum amount-of imide required would be (X+1)P mgs. per 100 cc. of concentrate and 10(X-l-l) (100P) mgs. per 100 cc. concentrate, respectively, where, X is the volume of diluent to be used per unit volume of concentrate in the subsequent dilution to yield the desired fly spray, and is the amount of p lfiethrum desired in the fly spray and should be from about 5 to about 109 mgs. per.100 cc. of fly spray.

Thus it will be seen from the above that the weight ratio of pyrethrum to imide in the preferred compositions of the invention is expressed by the fraction P/l0(l00P). Since the minimum amount of pyrethrum required is 5 mgs. per 100 cc. of spray, the weight ratio 'of pyrethrum to imide of at least l/lQQ-should bepresent in the preferred compositions of this invention.

The following tables illustrate the results obtained with a typical. composition of the inven-v tion using some. ofv the more effective imides.

PRESENTATIVE 'cLAssEs OF IMIDES 'PAELE I-niide's. of 3,65andomethy Compound at 2% in Q ..fly spray base,

Y Amount of Pyrethrum' (lontrolalyrethruxh None 30 mg.

N-n-propy N-n-dodecy N -cyclohexy N-phenyl N-beta-cyanpethyl; N-allyl N-omega-cyanoamyl...

Compopnd at 2% i n fly spraybase, Amount, ofv Py- Y rethrum V Controls, iyrethrum None, ing. 40mg. N'one 30mg. "mg. 100mg.

N 89-58 98-95 19-5 N 85-39 99-95 79 5 N 83-4 79-5 N 78-7 79-5 79-5 @ABLE I I'mides of mal eic acid b%mpoungi ai.2 ins y spra ase, YY Amount PF} Controls, Pyrethmm rethrum None 30mg. 40mg. 100mg.

N n-buty l I Nqs th lh xyl' vuuv .n H V A s 9 53 N-p-ethoxy-phenyl V 0 Y 47-12 N -phen'yl I 72-29 N-alpha-naphthyh- Y 13-0 N-o-toly 71-55 N-m-tolyl 74-57 Napqmlyl .M h 6 N -mixedvo-, 111-, and p-tolyl Y Y N-p-n-dod eey l phenyl I 1-0 N-o-nitrd-pheny Y 0-0 N-m-nitro-nhenvl 7 Y P Y 1-0 1 N-o-bipheny 2-0 N=viny1phth8limide Y 34-2 N-methallyLphtha limide" v 98-30 N-c'yclohexyl'phflialimidn Y Y 13-0 98-38 N-o-ethoxy-phenyl-phthalimide. Y 98-38 TABLE VII Miscellaneous-mike Cgmpound at. 212% in i jgf 15;; Gbntro]s,1 'yrethi'uin rethrum None 301312. 40mg. None mg. mg. 100mg,

N-n-vinylsvinnihimide 0 h 8 96-13 96-17 N-n-amylqnnninimme- V 97-25 98-44 N-n-oets lsuccinifilid'e -13 2-0 81-2 N-n-dcdecyL- Y- -V Y 94-28 Y Y Y 98-44 N-phenyl-alpha chloro smfimmiflfi TABLE VIII Geimpoundat 212% in Y.- pr y. ase V Y Amount or Controls, Pyrethmm rethrum Y None 30mg. 40mg; None 30mg. 40mg; mg.

N-ethyl snvvhnrim Y Y Y 7 Y r Y 90-48 Y 80-6 98-31 N-allyl saceharih Y 94-86 80-6 98-31 N-n-amyl sacehanirfii; 8 Y Y Y Y 96-53 Y 80-6 98-31 N-benzyl sacchar 92-24 '93 6 80-6 98-31 Mixed N-aniyl-homobmhmi'miflp 2 .0 9 3 NOTE: The first figure in the above-Columns iepisent's paralysis after 10 fninutes, and the figure after the hyphen i'ei resents the percent kllleclgf er 2A hangs eecerding to the Standard Feet-Grady. method of evaluetibn. V 7 4 ThelQO h II; pyrethmtn cont'rolis the oflicial test insecticide. In the other instances the earner or fly spray base ls-a. prqprletaryrefined kemsene (Deebase); V I

The data; in the tbs]; eogumnlwithqut giyiethwm) weretaken in amodifieatienpf the Peat-Grady test difier'mg prmezpally 1n the volume bf spray (15 00,) and time of exposure (15 minute? as Well as the classification of paralyzed files v c A number of the abv imides were insoluble a1: 2% in eobase-kerosene a'rgd required the assistance of a bl'endin solvent t'o on1- plete solution. Tep percent giioxame was use d ineonngcti on with the sompoimds marked wxth (*1 in grd'er to form ate a satlsfactor'y l1 11- Appr x t ly dibxali was used in connegtzion with those, compounds marked wlth GP) and approxlmately 30% dioxan'e with those marlid The data given in the following table are;

illustrative of compositions containing various" mixtures of n-butyl imide of 3,6-endomethylene- 4-cyclohexene-1,2-dicarboxylic, acid with pyrethrum in a fly spray base hydrocarbon solvent. These compositions are-comparable in efficiency to the standard 100 mg. flysprays (class B), or the equivalent, which are available on the open market. The data illustrate the marked synergism of the imide pyrethrum mixtures. If only the additive effects were involved the composition curve would be a linear one, ranging from the 2000 mgs. or moreof the imiderequired to equal the kill of the 100 mg. pyrethrum spray to the 100 mgs. of pyrethrum. Hence the theoretical composition may easily be calculated, for example, if the mixture contains only 40% of the pyrethrum (40 mg./ 100 cc.) necessary to give the standard class B fly spray it should contain 60% of the imide required to equal the kill of TABLE IX Actual Composigg Theo Perggiagiigml r6103, mt1on,Mg./l00 cc. position Percent; Abovle gstandage Control 7 Pyreth- Pyrcth- Innde mm Imide mm O'VII PTI 0 100 98-28 0 +9 0 100 98-35' 0 0 o 100 98-41 0 0 o 100 98-44 0 -4 0 100 98-37 0 0 0 100 98-26 0 +8 .420 40 1, 3g 98-30 +4 +4 0II=OfE1cial test insecticide (100 mgs. pyrethrum); PTI=Proprietary test insecticide (pyrethrum activated Wlth N-isobutylamide oi undecylenic acid).

1 Kill for OTI unusual 1y low.

of flies, as mosquito repellents, and for combatting like pests subject to control by household It will be observed from the data ene-4-cylohexene- 1,2-dicarboxy1ic imide gave 03% kill and 0% defoliation and was equally effective at one half concentration; N-benzyl-3,6- endomethylene 4-cyclohexene 1,2-dicarboxylic imide gave 100% kill and 0% defoliation and gave equal results at one half the concentration; N-ethyl saccharin gave 100% kill and 5% defoliation and equal results at one half the concentration; N-allyl saccharin gave 100% kill and 0% defoliation and substantially the same results. at one half the concentration; N-n-butyl- 7-methyl-3,6 endomethylene -4-cyclohexene-1,2- dicarboxylic imide gave 100% kill and 0% defoliation; N-n-butyl-hexahydrophthalimide gave 97% kill and-0% defoliation;- and N-o-tolyl maleimide gave 83% kill and 0% defoliation.

It will be understood that'the tertiary diacyl amines suitable for use in the compositions of the invention may be incorporated with various adjuvants, toxicants, and other ancillary agents, but whether the control of particularpests involved be realized as a result of ingestion, contact, or repellent action, the prime requisite is that the activeingredient be in a suitable form of dispersion to make possible efiective contact of the pest with the active agent or its vapors as the case may demand.

Those conversant with the pest control art know the particular adjuvants, toxicants, and ancillary agents which may be combined with a suitable toxicant or combination of toxicants to yield a composition suited'to the control of a particular insect, having in mind the nature of the insect, its particular, habitat and feeding habits and its peculiar susceptibilities, if any. I have found that insecticidal adjuvants can be combined similarly in various formulations with tertiary diacyl amines to yield new and effective in the presentation of an insecticidal material to an insect. The term adjuvant is well established in the art where it is recognized that an ine secticidal agent or toxicant is in itself of little practical utility for combatting insects unless .it be presented in a form suitable for effecting intimate contact of the agent or its vapors, as the particular case may require, with the insect. Thus'addi-tional material or materials'are employed in the formulation of an active ingredient to yield a suitable pest control composition, such materialsv being adjuvants. It will be appreciatecl, however, that materials which would be sprays, the invention is not so limited because many of the imides ShOW' toxicity, though in a lesser degree, to other insects such as red spider, aphids, clothes moths and Mexican bean beetles. For example, when applied in the form of a 1% talc dust to bean plants infested'with'Mexican bean beetle larvae N-allyl-3,'6-endomethylene-3- isopropyl-6-methyl-4- cyclohexene 1,2-dic'arbo'xylic imide gave 83% kill with only 2% defolia is preferably arefined kerosene.

toxic to warm blooded animals, would effect plant injury, or have other undesirable qualities at the concentrations and under the conditions to be employed are'generally unsuitable as adju'vants.

Preferably the tertiary diacyl amines may be utilized in the form of solutions in a suitable solvent, dust compositions, or slurries or emulsions in water according to the requirements of control of the particular insect involved. In'the'case'of'solutions of the activefagent in a solvent, the adjuvant may be'a hydrocarbon and The adjuvant employed when a dust composition is desirable may be selected from the class of finely divided solids comprising talcs, pyrophyllite, natural clays, and diatomaceous earth, such materials having 'a frequency particle size less than 50 microns: When it is desirable to use the insecticidal composition as a slurry dispersed in water then the composition i produced preferably in the form of a powder containing one of the adjuvants common to the dustbompositions described.

- above, said powder then being. dispersed tor actual usage water, usually withthe aid of awetting agent or dispersing agent. l

If the insecticidal composition is liquid to be used in the form of a dispersionor an emulsion inwa-ter;. then it ispreferred to prepare a relatively concentrated composition 1 of the active in a suitable solvent selected according to the-compound toheused, and: the use to whichitis:

to be put, or to prepare an emulsion of the activer agent ina non-solvent liquid in certain, cases where such technique is more'applicaioie, saidsom tions with such adjuvants as Spreaders, stickers,

diluents or extenders, and with other toxicants as may be most suited to the control of a particular pest or group. of pests; for example, insecticides such as metallic arsenates, fluosilicates, phenothiazines, 2,2-bis(para chlorophenyl) -1,1,1-trichloroethane and 2,2-bis(para-methoxyphenyl)- 1,1,1-trichlor0ethane, organic thiocyanates such as n dodecyl thiocyanate, fenchyl thiocyanoacetate and butyl Carbitol thiocyanate, nicotine, anabasine (moo-nicotine) nor-nicotine, rotenone and its congeners, hellebore, pyrethrum, N-isobutyluolecylenamide, aminomethyl sulfides, and bactericides and fungicides such as sulfur, polysulfides such as lime-sulfur, phenols, aminomethyl sulfides, copper acylacetonates, copper chelates of beta-keto acids and esters, copper chelates of salicylaldehyde, Burgundy mixture, Bordeaux mixture, the so-called insoluble coppers such as basic copper sulfates, copper oxychlorides, copper calcium chlorides, copper oxides, copper silicates, copper zeolites, and copper thiocyanates, the long-chain quaternary ammonium halides and derivatives of dithiocarbamic acid such as ferric dirnethyldithiocarbamate. 4

The compositions of the invention may also include tertiary diacyl amines with adjuvants such as calcium" phosphate, sulphur, lime, flours such as walnut shell, wheat, redwood, soya bean, cottonseed, or with organic solvents such as trichloroethylene, tetrachlorethylenc, Stoddard solvent, and other hydrocarbon solvents. They may be used in vegetable and mineral oil sprays in which petroleum or vegetable oil glycerides are used as contact agents or active poisons. Various adhesive and sticking materials such as rosin and glue may be used. Such mixtures with insecticides and fungicides and insecticidal and fungicidal adjuvants as are here set out may have particular usefulness in special applications and frequently will give better results than would be anticipated from the killing power or repellent action of each ingredient when used alone.

Broadly, suitable compositions may be prepared with the tertiary diacyl amines in a state of composition, sub-division, and association with other materials such as have been mentioned, such as may be necessary peculiarly to adapt the tertiary the chlorinated diacyl aminesrtorthe purpose tc be efiected, Itisi more specifically desired, however, to employ the:

tertiary diacyl amines in admixture; in compos-i-- tions containing insecticidal adjuvant selected from the group consisting of a hydrocarbon solvent, a talc haying a frequency particle siz less than 50 microns, and a sulfated higher alcohol.

The term insecticidal composition'used herein has the same meaning as the term insecticide as defined section 60f the Insecticide Act of 1910.- Thus the term insecticidal composition refers to any substance or mixture of substances intended to be used for preventing, destroying, repelling, or mitigating any insects which may infest vegetation, man or other an imals, or households, or be present in any environment whatsoever.

I use the term insect" herein in the same sense as defined in the Insecticide Act of 1910, section 6, wherein it includes the small invertebrate animals belonging to the class Insecta, as well as other allied classes of arthropods whose members are Wingless and usually have more than six legs, as spiders, mites, ticks, and centipedes.

I claim:

1. An insecticidal composition containing as an essential active ingredient in solution in kerosene, a tertiary diacyl amine represented by the formula in which XR Y is a diacyl radical and R is a monovalent organic radical linked to the nitrogen atom thru a carbon atom.

2. An insecticidal composition containing as an essential active ingredient in solution in kerosene, a tertiary diacyl amine representedby the formula in which R is o-benzo and R is a monovalent organic radical linked to the nitrogen atom thru a carbon atom.

3. A fly spray composition comprising a solution of pyrethrum and a tertiary diacyl amine represented by the formula in which R is o-benzo and R is a monovalent organic radical linked to the nitrogen atom thru 1'5 16 a carbon atom, the weight ratio of said' pyre- Number Name Date" thrum to said tertiary diacyl amine in said 2,304,830 Katzman Dec. 15, 1942 composition being at least 1/190. 2,389,427 Gertler Nov. 20, 1945 1 JAMES E. KIRBY. I 2,424,220 Bousquet July 22, 1947 1 5 OTHER REFERENCES REFERENCES CITED h Vanags:C emical Abstracts, vol. 34 (1940) The followmg references'are of record m the pages 19824983. (copy in R O. s L) file 9 thls patent: McA11ister:J. Economic Entomology, Dec.

7 UNITED STATES PATENTS m 1930, vol 23, pages 901-913, 9113. (Copy in Div. Number Name Date 1,961,840 Bolton June 5, 1934 oap and Samtary Chemicals (Jan. 1943, pages 2,119,701 callsen' June '7, 193 95 and 96 by RoarckLKCopy in Patent Office.)

2,205,558 Flett June 25, 1940 

1. AN INSECTICIDAL COMPOSITION CONTAINING AS AN ESSENTIAL ACTIVE INGREDIENT IN SOLUTION IN KEROSENE, A TERTIARY DIACYL AMINE REPRESENTED BY THE FORMULA 